Alkenyl mercury mercaptides



ALKENYL MERCURY MERCAPTIDES Albert L. Flenner, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Dei., a corporation of Delaware No Drawing. Filed Apr. 20, 1959, Ser. No. 807,297

Claims. (Cl. 260-431) This invention relates to new and useful fungicidal and polymerizable monomers of the formula: V

( 1 R'HgSR Where R is a lower alkenyl radical and R is a hydroxylated monovalent aliphatic or a hydroxylated monovalent cycloaliphatic radical bearing from 2 to 18 carbon atoms.

Preferably, R is a monovalent hydrocarbon radical containing at least one hydroxyl group and bearing from 2 to 18 carbon atoms selected from the class consisting of alkyl, alkenyl, and cycloalkyl radicals with the proviso that each carbon atom of such radical can at most have but one hydroxyl group and the carbon atom attached to sulfur has no hydroxyl groups.

Still more preferably R is an alkyl or an alkenyl radical bearing from 2 through 6 carbon atoms and from 1 through 5 hydroxyl groups with the proviso that each carbon atom can at most have but one hydroxyl group and the carbon atom attached to sulfur will have no hydroxyl groups.

When R is a hydroxylated monovalent aliphatic or cycloaliphatic radical, such radical can be substituted with various substituents in addition to being substituted with one or more hydroxyl groups. As used in this application, the term lower has reference to no more than 6 carbon atoms. 4

Thus R can be hydroxyethyl, hydroxypropyl or dihydroxypropyl, or R can be a butyl, pentyl or hexyl radical in which one or more carbons bear hydroxy radicals, such as hydroxybutyl, hydroxypentyl, hydroxyhexyl, dihydroxybutyl, tetrahydroxypentyl, pentahydroxyhexyl, or trihydroxyhexyl. R can also be hydroxynitroethyl, hydroxycyanobutyl, hydroxyfluorohexyl, hydroxychloroethyl, 3-ethoXy-2-hydroxypropyl. Likewise, R can be octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, pentadecyl, which can be hydroxylated in one or more positions and be substituted in one or more positions with groups such as nitro, cyano, chloro, bromo, fluoro, methoxy, or ethoxy. Also, R can be, for example, 4-hydroxy- 2-butenyl, 4-hydroxy-3-methyl-2-butenyl, or 4-hydroxy- 3-(hydroxymethyl)-2-butenyl. R can also be a hydr'oX'ylated alkenyl substituted in one or more positions with groups such as nitro, cyano, halogeno, methoxy, or ethoxy. Likewise, R can be a hydroxylated monovalent cycloaliphatic group such as cyclobutyl, cyclopentyl, cyelohexyl, or indanyl, hydroxylated in one or more positions and either substituted or unsubstituted in one or more positions with groups such as those set forth above.

Similarly, R can be a monovalent lower alkenyl radical having from 2 to 6 carbons, at least one double bond, and can be either substituted or unsubstituted with any of a wide variety of substituents. Thus R can be a lower alkenyl radical such as vinyl, allyl, 2-butenyl, 3-butenyl, hexenyl, chlorovinyl 4-hydroxy-2-butenyl, 4-h'ydroxy-3- methyl-Z-butenyl, or 4-hydroxy3-(hydroxymethyl)-2- butenyl. Likewise, R can be but'adienyl Z-(fl-chloroethyl)vinyl, butoxyvinyl, methoxyvinyl, nitrovinyl, chlorovinyl, cyanovinyl and the like.

attain? Patented Jan. 3, 1961 These new compounds of the present invention are readily made by reacting an alkenyl mercury salt with the appropriate mercaptan. The following equation illustrates the reaction:

wherein R and R have the same significance as above indicated and X is hydroxy or the anion of an acid.

The reaction is slightly exothermic. The reaction is best carried out in an inert medium in which the reactants are soluble. Water, methanol, ethylene glycol, ketones, and the like can be used as this medium. The reaction can be promoted by agitating or shaking the reactants to obtain rapid and thorough mixing. If pure products are desired X- is preferably hydroxy, and the products can be obtained by repeated crystallization from solvents such as the above.

As noted, these new compounds have fungicidal utility and can be applied in the ways conventionally known and used in the art for the protection of organic matter from fungus infestation. Thus they can be used, for example, for the protection of carbohydrates, proteins and hydrocarbon oils. More specifically, they can be used, for example, to treat living plants such as fruit-bearing trees. Also they can be used to treat organic fibers or fabrics and cellulosic materials such as leather and wood. Like- Wise, they can be used to treat paints, lubricating oils,

and oil-drilling muds to protect such materials from fungus attack. Also the compounds of the invention can be used for purposes such as slime-control in paper mills, water-cooling towers and the like. The compounds are especially useful in treating seeds prior to planting so as to prevent fungus infestations by soil borne or seed borne fungi, with the result that high percentage of seed germination results and that seedlings emerge free of fungus disease.

When the compounds are used as above as fungicides, they can be formulated in the conventional manners known and used in the art.

Because these fungicidal compounds also have the unusual capacity of being co-polymerizable with other ethylenically unsaturated monomers to give polymers containing mercury as part of the polymer matrix, these new compounds can be prepared into the form of fungicidal copolymers, for example, for use in latex paints. Mercurial fungicides are conventionally used in polymers, protective coatings, films, paints and the like by being incorporated into the vehicle or the solvent after polymerization of the resin and during the so-called compounding or formulation step. The fungicide thus is present as a dispersion or as a solution and is not attached to the mixture by chemical forces. The alkenyl mercury compounds, on the other hand, when co-polymerized with the resin, are attached by chemical bonds into and throughout the body of the resin or polymer, thus protecting it against attack by mildews, other fungi, bacteria, and the like. By thus forming an integral part of the polymer the fungicide resists weathering or leaching and the mercury-containing polymer is intrinsically fungus-resistant.

This application is a continuation-in-part of my copending U.S. applications Serial No. 409,771, filed February 11, 1954, now abandoned; and Serial No. 498,754, filed April 1, 1955.

The invention is further illustrated by the following examples in addition to those given above.

EXAMPLE 1 YA solution containing 24.47 grams of vinyl-mercury hydroxide and 200 ml. of methanol is prepared. To

this solution is added 10.8 grams of thioglycerol. The mixture is vigorously agitated for about ten minutes,

Percent vinylmercury 2,3-dihydroxypropyl mercaptide 4.0 Water 45.0

Ethanol 20.0 Ethylene glycol 30.0 Rhodamine dye 1.0

EXAMPLE 2 Percent Butenylmercury 2,3-dihydroxypropyl mercaptide 1.0 Ethanol 68.0

Ethylene glycol 30.0 Rhodamine dye 1.0

This fungicidal composition when sprayed upon wheat seed at a dosage of 3 oz. per bushel is highly effective In controlling fungus growth on the seed.

EXAMPLE 3 The hexylmercury salt of 2,3-dihydroxypropyl mercaptan is prepared in accordance with the procedures set forth in Example 1 but using a molar equivalent amount of hexylmercury hydroxide in place of the vinylmercury hydroxide employed in Example 1. This compound is a solid that is soluble in alcohol.

The hexylmercury salt of 2,3-dihydroxypropyl mercaptan is then formulated into a fungicidal composition substituting it for the fungicidally active ingredient of the formulation of Example 2.

This fungicidal composition when sprayed upon wheat seed at a dosage of 3 oz. per bushel is highly effective in controlling fungus growth on the seed.

EXAMPLE 4 The allylmercury salt of 2,3-dihydroxypropyl mercaptan is prepared in accordance with the procedure set forth in Example 1 but using a molar equivalent amount of allylmercury hydroxide in place of the ethylmercury hydroxide employed in Example 1. This compound is a white crystalline solid that is readily soluble in alcohol.

The allylmercury salt of 2,3-dihydroxypropyl mercaptan is then formulated into a fungicidal composition by substituting it for the fungicidally active ingredient of the formulation of Example 1.

This fungicidal composition when sprayed upon wheat seed at a dosage of 3 oz. per bushel is highly effect1ve in controlling fungus growth on the seed.

EXAMPLE 5 The allylmercury salt of hydroxyethyl mercaptan is prepared in accordance with the procedure set forth in Example 1 but using a molar equivalent amount of allylmercury hydroxide in place of the ethylmercury hydroxide and hydroxyethyl mercaptan instead of the thioglycerol employed in Example 1. This compound is a solid that is soluble in alcohol.

This product can be used in a seed treatment formulation similar to that of Example 1 which, when sprayed upon wheat seed at a dosage of 3 oz. per bushel is highly effective in controlling fungus growth on the seed.

EXAMPLE 6 Vinylmercury 2,2-dihydroxyisopropyl mercaptide is prepared in accordance with the procedure set forth in Example 1 but using molar equivalent amounts of 2,2- dihydroxyisopropyl mercaptan in place of the thioglycerol of Example 1. This compound is a solid that is soluble in water and alcohol.

The vinylmercury salt of 2,2'-dihydroxyisopropyl mercaptide is then formulated into a fungicidal composition by substituting it for the fungicidally active ingredient of the formulation of Example 1.

This fungicidal composition when sprayed upon wheat seed at a dosage of 4 oz. per bushel is highly effective in controlling fungus growth on the seed.

EXAMPLE 7 Allylmercury 2,2'-dihydroxyisopropyl mercaptide is prepared in accordance with the procedure set forth in Example 1 but using molar equivalent amounts of allylmercury hydroxide and 2,2'-dihydroxyisopropyl mercaptan in place of the reactants of Example 1. This compound is a solid that is soluble in water and alcohol.

The allylmercury salt of 2,2'-dihydroxyisopropyl mercaptide is then formulated into a fungicidal composition by substituting it for the fungicidally active ingredient of the formulation of Example 1.

This fungicidal composition when sprayed upon wheat seed at a dosage of oz. per bushel is highly efiective in controlling fungus growth on the seed.

EXAMPLE 8 Vinylmercury-gluco-2,3,4,5,6-pentahydroxyhexyl mercaptide is prepared in accordance with the procedure set forth in Example 1 but using molar equivalent amounts of gluco-2,3,4,5,6-pentahydroxyhexyl mercaptan (thiosorbitol) in place of the thioglycerol of Example 1.

This compound is solid that is soluble in water and alcohol.

The vinylmercury salt of gluco 2,3,4,5,6-pentahydroxyhexyl mercaptan is then formulated into a fungicidal composition of the following ingredients:

Percent Vinylmercury gluco 2,3,4,5,6-pentahydroxyhexyl mercaptide 4.0 Water 47.5 Ethanol 47.5 Rhodamine dye 1.0

This fungicidal composition when sprayed upon wheat seed at a dosage of A 02. per bushel is highly effective in preventing fungus growth on the seed. This composition is also highly effective in controlling fungus growth on flax and sorghum seed.

EXAMPLE 9 This example illustrates the formation of a copolymer of an alkenylmercury hydroxyalkyl mercaptide with vinyl acetate and its utilization in finishes formulations.

A solution comprising 10 parts allylmercury 3,2-dihydroxypropyl mercaptide and drying and then redissolving the copolymer in suitable solvents.

about ten minutes and the resulting product produced is then isolated by evaporating the methanol solvent under The copolymer produced by the above procedures may vacuum.

Table I Mercury Reactant Mercaptide Reactant Alkenyl Mercury Mercaptide Product Vinylmercury hydroxide 2,3,4,5,6-pentahydroxyhexyl mercap- Vinylmercury 2,3,4,5,6-pentahydroxytan. hexyl mercaptide. 11 butadienylmercury hydroxide dihydroxypropyl mercaptan butadienylnercury dihydroxypropyl mercap 1 e. 12 hexenylmercury hydroxide. 2-hydroxyethyl merca-ptan hexen ylimercury 2-hydroxyethyl mercap 1 e. 13 eyanovinylmereury hydroxide gluco-2,3,4,5,6-pentahydroxyhexyl cyanovinylmercury gluco-2,3,4,5,6-

mereaptan. pentahydroxyhexyl mercaptide. 14 allylmercury hydroxide 2,3,4,5tetrahydr0xypentyl mercaptan. allylmercury 2,3,4, 5-tetrahydroxy peutyl mercaptide. 15 Vinylmercury hydroxide 2,2-dihydroxyisopropylmercaptau vinylmertqgry 2,2-dihydroxypropy1 mercap 1 e. 16 2-butenylmercury hydroxide 1-hydroxy-2-mercaptobuteue-B 2-butenylmercury-1'- hydroxy'methyl- 2-propenyl mercaptide. 17 chloroethylvinylmercury hydroxide.-. 2-hydroxy-cyc1ohexylmercaptau ch10roethylvinylmercury-2-hydroxycyclohexyl mercaptide. 18 allylmercury chloride 9,10-dihydroxyoctadecylmercaptam-.. allylmercgay-QJO-dihydroxyoctadecyl mercap 1 e. 19 Vinylmercury hydroxide 1,3,5-trimethyl-2-hydr0xyocty1 mer- Vinylmercury 1,3,5 trimethyl 2 hy captan. droxyoctyl mercaptide. on do hexahydro-5,6-dihydroxy-4,7-methane Vinylmercury hexahydro-fi,6-diindan-l-yl methyl mercaptan. hydroxy 4,7 methane indan 1 yl methyl mercaptide. 21 3-butenylmercury hydroxide 2 meth0xy-3-hydroxypropyl mercap- 3-butenylmereury-2-methoxy-3-h ytan. droxypropyl mercaptide. 22 4-hexeny1mercury acetate 9,10-dihydroxydecylmeroaptan 4 hexenylmercury 9-10 dihydroxy.

decyl mercaptide. 23 allylmercury hydroxide thioglycerol allylmerg zlry-2,3-d1hydroxypropy1 mercap 1 e. 24 methoxyvinyl mercury hydroxide 1,3,5,7-tetramethyl-2-hydroxyoctyl methoxyvinylmercury-l,3,5,7- tetramercaptan. methyl-2-hydroxyoctyl mercaptide. 25 chlorovinylmercuryhydroxide 2,3,4,5,6peutahydroxyhexyl mercapchloroviny1mercury-2,3,4,5,6-pentatan. hydrpxyhexylmercaptide. 26 nitrovinylmercury hydroxide dihydroxypropyl mercaptan nitrovmytlglercury dihydroxypropyl rrercap 1 e. 27 e-hydroxy-2-buteny1mercury hy- 2-hydr0xy-3-ethoxypropyl mer- 4-hydroxy-2-buteny1mercury-2-hydroxide. captan. droxy-3-ethoxvpropyl n ercaptide. 28 4-hydroxy-3-methyl-2-butenylmer- G-hydroxyhexyl mercaptan 4-hydroxy-3-methy1-2-buteny1mercuryoury hydroxide. fi-hydroxyhexyl mercaptide. 29 4-hydroxy-3-(hydroxy methyD-Z-bugluc0-2,3,4,5,G-pentahydroxyhexyl 4-hydroxy-3-(hydroxyrrethyD-2-butenylmercuryhydroxide. mercaptau. tenyi mercury g1uc0-2,3,4,5,6-pentahydroxyhexyl mercaptide. 30 2-hexenyl mercury hydroxide (2-hydroxyoctyl) (Q-hydroxyuonyD- 2-hexenyl mercury (-2-hydroxyoctyl)- methyl mercaptan. (Q-hygrQXynonyD-methyI mercap 1 e.

be used as the sole film forming vehicle, both with and without added pigments, extenders, and other agents, to give decorative and protective finishes for all types of substrate surfaces. It may also be blended into drying oils, varnishes and resinous paint vehicles to give compositions having greatly improved resistance to decay by EXAMPLES 10-30 Other alkenyl mercury mercaptide compounds within the scope of Formula 1 above are prepared by reacting a suitable organo mercury reactant with the appropriate mercaptide reactant using a mole ratio of 1:1. The mercury reactant is first dissolved in excess methanol and then the mercaptan reactant is dissolved in the solvent mix. Next the mixture is agitated vigorously for The claims are: 1. A compound of the formula where RHgSR R is an alkenyl radical containing from 2 through 6 carbon atoms and R is a monovalent hydrocarbon radical containing at least one hydroxyl group and bearing from 2 through 18 carbon atoms and selected from the group consisting of alkyl, alkenyl, and cycloalkyl radicals, with the proviso that each carbon atom of the radical can have at most but one hydroxyl group and the carbon atom attached to sulfur has no hydroxyl groups.

2. Vinylmercury 2,3-dihydroxypropyl mercaptide.

3. Butenylmercury 2,3-dihydroxypropyl mercaptide.

4. Vinylmercury gluco 2,3,4,5,6 pentahydroxyhexyl mercaptide.

5. Allylmercury 2,3-dihydroxypropyl mercaptide.

References Cited in the file of this patent UNITED STATES PATENTS 2,618,645 Bowles Nov. 18, 1952 Hartmann et a1. May 31, 1949 i UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent N00 2367 191 January 3 1961 Albert La Flenner It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below Column 6 line 42, etrike out "where" and insert the same in line 44L same column, above "R is in 1ine: 4L.5a

Signed and sealed this 23rd day of May 19615 (SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents 

1. A COMPOUND OF THE FORMULA WHERE 